The complicated photophysics of wide variety of defects existing in silica (SiO 2 ) layer of nanometer thickness determines widespread photoluminescence bands of Si/SiO 2 based system as well as SiO 2 nanoparticles (NPs) for their applications in photovoltaic and optoelectronic devices. This review attempts to summarize different photophysical processes in pure SiO 2 NPs. Moreover, these NPs also act as scaffolds for various guest molecules to perform their specific functions. Guest fluorophore molecules when trapped inside pores of SiO 2 NPs exhibit a different photodynamics than free state, which opens up several important applications of hybrid SiO 2 NPs in artificial photosynthesis, sensing, biology and optical fiber.